It is known to prepare halogenated diphenols which can be used as anti-mildew agents, fungicides, fire retardant agents in various polyesters, monomers for the preparation of aromatic polycarbonates, and the like.
The preparation of halophenols, including halodiphenols, halotriphenols, halotetraphenols, etc., is often desired to improve the properties of the parent phenol. For instance, the halogenated phenols often possess enhanced, desirable biological properties, compared with nonhalogenated phenols and have been manufactured on a large scale. For example, pentachlorophenol is potent wood preservative, pentabromophenol is a component of flame retardant formulations, 2,2'-methylenebis(3,4,6-trichlorophenol) is a potent and useful bactericide, and 4,4'-isopropylidenebis(2-chlorophenol) has been used as an anti-mildew agent. Often, derivatives of halophenols are also useful such as polymers derived from 4,4'-isopropylidenebis(2,6-dibromophenol) and the corresponding bis(dichlorophenol) which, in the form of polyesters and polycarbonates, possess outstanding flame-retardant characteristics as is known in the prior art.
The preparation of halophenols is customerily carried out by direct halogenation with elemental chlorine and/or bromine. In the case of simple or stable molecules, this appears to be the simplest process. However, when it is applied to more complicated and sensitive structures, it often yields by-products that can seriously interfere with the intended end-use of the halophenols. For instance, U.S. Pat. No. 3,062,781 discloses halogenated diphenols which are obtained by a direct halogenation procedure which require further treatment with sodium hydroxide and triethylamine at 80.degree. C. before they can be converted to polycarbonates of acceptable stability. Such a treatment is necessary in order to remove aliphatically bound halogens formed in the halogenation process. It has been found that these aliphatically bound halogen compounds, which are generally recognizable by their red color, are formed by the cleavage reaction exerted by the hydrogen halide coproduct on the diphenol. For example, when 4,4'-isopropylidenediphenol (BPA) is employed, the chlorination reaction produces an equimolar amount of hydrogen chloride coproduct as shown below: ##STR1## The HCl coproduct produced in (I) above effects a cleavage reaction on BPA or its chlorinated derivatives as shown below: ##STR2## Thus, the chloroisopropylphenols cause the discoloration and the chlorinated phenols also have a disagreeable odor. The formation of by-products is even more pronounced in bromination processes.
German Pat. No. P25 317.2 discloses two methods for brominating and/or chlorinating bisphenols; namely, a gas-solid phase method and a suspension method. From these methods, there are obtained a mixture of unreacted bisphenol and statistical mixtures of halogenated bisphenols which are used to prepare polycarbonates having improved fire retardant properties.
In the suspension method disclosed in this German patent, the bisphenol is suspended in a halogen-containing hydrocarbon to produce a halogenated bisphenol. The halogen-containing hydrocarbons disclosed are carbon tetrachloride and tetrachloroethane, carbon tetrachloride being preferred.
While the suspension method disclosed in the above-identified German patent is of interest, it is not entirely satisfactory. For example, since bisphenols are not very soluble in either carbon tetrachloride or tetrachloroethane, excess halogen, i.e., either bromine and/or chlorine, must be used to assure halogenation of the bisphenols. As a result, a significant amount of halogen is lost in the system during the reaction and the rate of halogenation cannot be closely controlled. Thus, this method produces an excess of unreacted bisphenols and, primarily, tri- and tetrahalogenated bisphenols which, when further processed to produce a polycarbonate, do not impart good impact properties to the polycarbonate. Furthermore, the halogenated bisphenols must be isolated from the solvent system before they can be subjected to polymerization to obtain polycarbonates.
Co-pending application Ser. No. 882,192, filed Feb. 28, 1978, and assigned to the same assignee as this case discloses a continuous process for producing high molecular weight polycarbonates including halogenating diphenols wherein the diphenol is dissolved or suspended in a solvent system comprising methylene chloride and water and metering a halogen gas into the solvent system. In that process, water is used to react with the hydrogen halide produced and thereby minimize the formation of undesirable by-products.
Co-pending application Ser. No. 882,242, filed Feb. 28, 1978, also assigned to the same assignee as this case, discloses a process for halogenating diphenols wherein the diphenol is dissolved or suspended in methylene chloride and then contacted with sulfuryl chloride which reacts with the halogen halide produced in a "self-sweeping" reaction thereby minimizing the formation of undesirable by-products. In this process, bromine can also be incorporated concurrently with the sulfuryl chloride.